JP5280481B2 - Method for dispersing insoluble material in aqueous solution and agricultural formulation - Google Patents

Abstract

A method of dispersing an insoluble material in an aqueous solution comprising the following steps: (i) providing a formulation comprising at least one insoluble material and at least one dispersant comprising a water soluble agriculturally acceptable derivative of an alternating copolymer or an agriculturally acceptable salt thereof wherein said alternating copolymer comprises at least one residue of a first comonomer and at least one residue of a second comonomer, wherein said first comonomer comprises alpha,beta-unsaturated oxyacids or anhydrides and said second comonomer comprises olefinic compounds containing one or more polymerizable double bonds; and (ii) dispersing said formulation in an aqueous medium.

Description

  The present invention relates generally to dispersants used in agricultural applications, and in particular, the present invention is a copolymer dispersion formed such that the dispersion has improved dispersibility and exhibits improved suspendability. The present invention relates to a method for dispersion of insoluble materials using agents. The invention also relates to a method of producing a dispersible formulation, the formulation itself, and a method of treating a substrate using a dispersion made from such a formulation.

  The active ingredients in many agricultural applications are largely hydrophobic or water-insoluble and are inevitably often suspended in aqueous media as finely divided solids. Most of these active ingredients are manufactured in a concentrated form and are commercially available, and also allow the addition of other insoluble and inert diluent fillers before being applied. For example, the active ingredients are generally available in the form of suspension concentrates (SC), wettable powders (WP), or granules that can be dispersed in water (WG). However, in order to obtain a uniform dispersion with minimal mixing, which can be easily achieved by hand or with minimal mechanical mixing, it is generally appropriate for the hydrophobic nature of the active ingredient to be adequate. Addition of a dispersant is essential. Furthermore, once a uniform dispersion is obtained, the resulting suspension must be kept stable for a sufficient time so that at least conventional means such as spraying can be used. Any settling, agglomeration or agglomeration of finely divided solids is limited to inconsistent and inefficient applications, as well as clogging of the spray device. Therefore, it is necessary to provide a dispersant that provides an easily and uniform dispersion and maintains its stability during use in aqueous dispersions.

  Effective dispersants used in these applications are those that ideally provide acceptable dispersibility, suspendability, and agglomeration free suspension. Collaborative International Pesticides Analytical Council (CIPAC Handbook Volume 1) is an acceptable suspension (MT15.1) and method used to measure the degree of aggregation (MT59.3) For example, in the concentration of suspensions in so-called SC formulations, this can be achieved by adding about 3.5 w / w% of a standard dispersant, wettable powder (WP) and Granule wettable powder (WG) formulations are on the order of 6-7 w / w% to achieve generally acceptable suspendability and cohesiveness as measured by wet sieve retention test (MT59.3). The addition of a standard dispersant is required.

  Dispersants widely used in SC formulations include ethylene oxide / propylene oxide block copolymer surfactants based on ethylene oxide plus a hydrophobic portion. In addition, ether phosphate derivatives of nonionic surfactants, particularly tristyrylphenol ethoxylate, are used. Common anionic surfactants used include sulfonated derivatives of aryl formaldehyde condensates, polyacrylates and lignosulfonates.

  Dispersants in WP and WG formulations are usually limited by the requirement that the dispersant is a solid at room temperature, does not gel, and does not dissolve in the active ingredient. For these reasons, common non-ionic surfactants are often not suitable and anionic dispersants are preferred. Well known and effective dispersants for WP and WG formulations include salts of sulfonated alkylnaphthalene / formaldehyde condensates, and salts of lignosulfonates.

Alpha-olefin-polycarboxylate copolymers are well known as dispersants in a wide range of applications including pigment dispersions, emulsion polymerization, cosmetics, and pesticide ingredients. As far back as 1972, the sodium salt of the copolymer of maleic anhydride and diisobutylene is available from Rohm and Haas Co. Following the application from the United States, the United States Environmental Protection Authority has been granted exemptions for acceptable amounts for use in pesticide formulations. FR 2 545 325 describes the use of ammonium and alkali metal salts of maleic anhydride-diisobutylene copolymers in pesticide particles. Similarly, EP 2014417 describes the use of maleic anhydride copolymers in WP and WG formulations with surfactants selected from sulfated and phosphates of ethoxylated phenol derivatives. JP 6203302 describes a copolymer having a molecular weight range of 5000-20000 for use with a granular agricultural chemical composition. Copolymer derivatives of maleic anhydride and diisobutylene are described in JP 0609,302 for use in SC formulations with CaCO ₃ and Mg salts. The use of sulfonated derivatives of maleic anhydride copolymers in water dispersible granules is also described in JP 58-131903.

  French Patent No. 2.397.444 describes a stable and concentrated dispersion of the active material prepared from non-dust or particulate material. Organic solvents that require separation of the active material in the presence of acidic resin salts, such as copolymers of maleic anhydride and α-olefin compounds, forming a two-phase system with an aqueous medium Treating the two-phase system by adding carrier material, and then adding water to gradually transfer the solvent into the water to reduce the volume of the organic phase. The product is separated.

(Disclosure of the Invention)
We have already described here in the prior art when using derivatives in the range of alternating copolymers of α, β-unsaturated oxyacids and olefins having one or more polymerizable double bonds. Has been found to provide improved dispersibility and suspendability to agricultural chemical formulations, as well as numerous other attendant advantages described herein, more fully compared to existing dispersants. It is.

  According to a first aspect of the present invention, there is provided a method for dispersing an insoluble material in an aqueous solution comprising the following steps.

(I) providing a formulation comprising at least one insoluble material and at least one dispersant of an alternating copolymer water-soluble agriculturally acceptable derivative or agriculturally acceptable salt thereof. The alternating copolymer comprises a residue of at least one first comonomer and a residue of at least one second comonomer, wherein the first comonomer is an α, β-unsaturated oxyacid. Or comprising an anhydride and the second comonomer comprises an olefinic compound containing one or more polymerizable double bonds;
(Ii) A step of dispersing the preparation in an aqueous medium.

  According to a second aspect of the present invention, there is provided a method of making an agricultural chemical formulation comprising the following steps.

(I) combining at least one insoluble material with at least one dispersant comprising a water-soluble agriculturally acceptable derivative of an alternating copolymer, or an agriculturally acceptable salt thereof, The alternating copolymer comprises a residue of at least one first comonomer and a residue of at least one second comonomer, and the first comonomer comprises an α, β-unsaturated oxyacid or anhydride. And wherein the second comonomer comprises an olefinic compound containing one or more polymerizable double bonds,

(Ii) pulverizing the combination material to a particle size range to obtain a stable, easily suspendable aqueous dispersion; and

(Iii) Stabilizing the aqueous dispersion to obtain an SC formulation suitable for dilution in water for agricultural use.

  In accordance with a third aspect of the present invention, there is provided a method of making an agricultural chemical formulation comprising the following steps.

(I) combining at least one insoluble material with at least one dispersant comprising a water-soluble agriculturally acceptable derivative of an alternating copolymer, or an agriculturally acceptable salt thereof. The alternating copolymer comprises a residue of at least one first comonomer and a residue of at least one second comonomer, wherein the first comonomer comprises an α, β-unsaturated oxyacid or anhydride. And wherein the second comonomer comprises an olefinic compound containing one or more polymerizable double bonds; and

(Ii) pulverizing the combination to the desired particle size to obtain a uniform wettable powder (WP) formulation.

  In accordance with a fourth aspect of the present invention, there is provided a method of making an agricultural chemical formulation comprising the following steps.

(I) combining at least one insoluble material suitable for agricultural use with at least one dispersant comprising an alternating copolymer water-soluble agriculturally acceptable derivative, or an agriculturally acceptable salt thereof. The alternating copolymer comprises a residue of at least one first comonomer and a residue of at least one second comonomer, wherein the first comonomer is an α, β-unsaturated oxy Consisting of an acid or anhydride and the second comonomer comprising an olefinic compound containing one or more polymerizable double bonds; and

(Ii) blending the combination to obtain a uniform wettable powder (WP) formulation.

  In accordance with a fifth aspect of the present invention, there is provided a method of making an agricultural chemical formulation comprising the following steps.

(I) combining at least one insoluble material suitable for agricultural use with at least one dispersant comprising an alternating copolymer water-soluble agriculturally acceptable derivative, or an agriculturally acceptable salt thereof. The alternating copolymer comprises a residue of at least one first comonomer and a residue of at least one second comonomer, wherein the first comonomer is an α, β-unsaturated oxy Consisting of an acid or anhydride, and wherein said second comonomer comprises an olefinic compound containing one or more polymerizable double bonds;

(Ii) agglomerating the combination to form separate granular materials; and

(Iii) drying the granular material to obtain a water dispersible granular WG formulation

According to a sixth aspect of the present invention there is provided a formulation produced by the process of the second, third, fourth and fifth aspects.
According to a seventh aspect of the invention, from at least one insoluble material and at least one dispersant comprising a water-soluble agriculturally acceptable derivative of an alternating copolymer, or an agriculturally acceptable salt thereof. Wherein the alternating copolymer comprises a residue of at least one first comonomer and a residue of at least one second comonomer, wherein the first comonomer is α , Β-unsaturated oxyacids or anhydrides, and the second comonomer is composed of an olefinic compound containing one or more polymerizable double bonds.

  According to an eighth aspect of the present invention there is provided a method of treating a substrate with an insoluble material comprising the following steps.

(I) preparing a formulation comprising at least one insoluble material and at least one dispersant comprising a water-soluble agriculturally acceptable derivative of an alternating copolymer, or an agriculturally acceptable salt thereof. The alternating copolymer comprises a residue of at least one first comonomer and a residue of at least one second comonomer, wherein the first comonomer is an α, β-unsaturated oxyacid. Or comprising an anhydride and the second comonomer comprises an olefinic compound containing one or more polymerizable double bonds;

(Ii) dispersing the formulation in an aqueous medium; and (iii) applying the dispersed formulation to a substrate.

  The dispersant used in the present invention is based on an alternating copolymer. It will be appreciated by those skilled in the art that alternating copolymers are prepared by careful selection of comonomers and reaction conditions. As is well known in the art, additional polymerization conditions are often observed to obtain alternating copolymers. For example, temperature and solvent type affect whether alternating or other types of copolymers are formed. Methods for making such alternating copolymers are well known to those skilled in the art of polymer synthesis.

  The alternating or substantially alternating properties of the copolymer are believed to be important to the present invention. It will be appreciated by those skilled in the art that a degree of regularity is required for the copolymer to be considered alternating properties. The alternating copolymer has alternating properties defined by 70% or more, more preferably 90% or more, continuous comonomer residue units that alternate between the residue of the first comonomer and the second comonomer. It is preferable. In the synthesis of such copolymers, a high degree of control is required in most cases to achieve this.

  The alternating copolymer can contain additional comonomer residues. For example, an additional small amount of methyl methacrylate, which can be 10% or less, will not substantially change the alternating properties of the copolymer. Suitable alternating copolymers for use in the present invention can also include copolymers of three or more comonomers, including first and second comonomer types. Without wishing to be bound by theory, if the consistent backbone of the hydrophobic polymer is regularly spaced anionic charge, or along the polymer molecule as obtained by alternating copolymers It seems that the improved dispersant performance is retained, given the presence of a stereochemical barrier.

  Copolymers having an anionic charge substantially regularly spaced along the polymer molecule provide excellent dispersant performance. For example, alternating or repeating units are preferably monomers, but can also be dimers, trimers, or small oligomers.

  Without wishing to be bound by theory, it is believed that the stiffness of the polymer molecule is related to its properties as a dispersant. The improved dispersant properties are believed to be related to the degree of steric hindrance and the resistance to free rotation of the polymer.

  The alternating copolymer can be made by polymerizing a first comonomer or a mixture of first comonomer with a second comomer, the first comonomer having at least one reactive double bond, The balance of substituents on the heavy bond creates an electron deficiency of double bonds compared to styrene (see Polymer Handbook, Section II / 267), which is often used by those skilled in polymer chemistry as a benchmark monomer. The comonomer has at least one double bond copolymerizable with the first comonomer, and the balance of substituents on the second comomer double bond is compared to the first comomer double bond. It creates a double bond that is electron rich.

  Examples of suitable preferred first comonomers include fumaric acid, maleic acid, and acid anhydrides, and esters, amides, and imides derived from them, itaconic acid and anhydrides, and the corresponding derivatives derived therefrom. Ester amides, and imides, acrylic acid and methacrylic acid, esters and amides, vinyl phosphonic acids and corresponding esters and amides derived therefrom, and ethylene sulfonic acids and esters and amides derived therefrom.

  Examples of preferred second comonomers include styrene and its alkyl and halo derivatives, vinyl ethers and esters, α-olefins, internal olefins, cyclic olefins, both exocyclic and endocyclic, allyl alcohol and its corresponding ester derivatives, Allyl ether and allyl halo compounds, allyl aryl compounds, vinyl amides, vinyl chloride and vinylidene chloride are included.

  While not wishing to be bound by theory, the electron deficiency and electron-rich double bond imbalance of the first and second comonomers is induced, as opposed to the characteristics of random or block homopolymerization. Give the copolymer substantially alternating properties. While not intending to be bound by theory, it appears that the alternating properties of the copolymer derivatives provide consistent charge density or steric barrier properties, aid dispersant properties, and also improve water solubility.

  The dispersants of the invention are alternating copolymers, agriculturally acceptable salts or water-soluble agriculturally acceptable derivatives, and preferably those that are readily soluble in water. Suitable agriculturally acceptable salt derivatives include acids and pendant groups of copolymers such as acid derivatives such as anhydrides and esters, alkali and alkaline earth metal hydroxides, oxides, carbonates. And alkoxides, or those obtained by reacting with basic reagents such as basic nitrogen, ammonia, amines and sulfur and phosphorus compounds such as tetraalkylammonium, sulfonium and phosphonium salts. Although salts of alternating copolymers that are acceptable for agriculture are generally preferred, the free acid of the alternating copolymer can be fed to the formulation and a different source of the appropriate cation and added to the aqueous medium to solubilize the alternating copolymer.

  Preferably a suitable cation amount is sufficient to provide optimum dispersant properties in the alternating copolymer. It is generally desirable to provide an excess of cations such that the alternating copolymer is a substantial amount to form a polyanionic polymer. Alternating copolymer acid anhydrides generally do not dissolve in water. However, we have found that the free acid exhibits some solubility in water. In one embodiment, the formulation can include an alternating copolymer free acid (in the absence of any suitable cationic material). The cationic raw material can be separately added and supplied to the aqueous medium before dispersing the preparation.

  It has been found that certain combinations of alternating copolymer free acids and cationic ingredients added separately prior to dispersing the formulation are advantageous. It is believed that the reaction between the free acid and the cation source generates gas and the action promotes the collapse of the granules contained in the insoluble material. In particular, the addition of sodium carbonate is accompanied by the generation of carbon dioxide and consequently promotes the collapse of the granules. Other cationic raw materials can be selected, resulting in a variety of gaseous reaction products and an improved dispersion.

  Cationic raw materials suitable for incorporation into either formulations or aqueous media include those of agriculturally acceptable cations such as alkali metal cations. Preferably the cationic source is selected from the group consisting of alkali salts such as carbonates, bicarbonates, hydroxides, phosphates, alkoxides, borates, sulfites, and silicates. Other water soluble agriculturally acceptable alternating copolymer derivatives include polyalkyleneoxy derivatives, polyamide derivatives, and polyvinyl alcohol derivatives. The expression water-soluble means that the derivative of the alternating copolymer is at least partially water-soluble at room temperature. Water soluble derivatives of other alternating copolymers are also useful in the present invention.

  The preferred molecular weight of the alternating copolymer is in the range of 1000 to 90000 daltons. We have found that some high molecular weight alternating copolymers are somewhat difficult to handle in solution, and our more preferred range is 1000-30000 daltons, and a more preferred range is 1000-10000 daltons.

  Agriculturally acceptable salts used as dispersants in agricultural compositions, or other water-soluble alternating copolymer derivatives, have been used conventionally such as sulfonated alkylnaphthalene formaldehyde condensate salts. We have found improved and consistent dispersant properties when compared to the agents.

  The copolymers described here give superior properties when compared to the dispersant structures already described in the prior art, such as diisobutylene, isobutylene and copolymers of styrene and maleic anhydride, and these same It is surprising that the other derivatives described in the publication cannot be adequately used as dispersants for agricultural applications at all. For example, we have found that some styrene-maleic anhydride copolymer derivatives result in poorly stable and in some cases unstable dispersions.

  Only the alternating properties do not seem to guarantee the effective properties of the dispersant copolymer, for example a copolymer of methyl vinyl ether and maleic anhydride gives an unstable dispersion. Without wishing to be bound by theory, this is likely due to the presence of a small hydrophobic backbone, low molecular weight, or a combination thereof.

  Similarly, some linear α-olefin maleic anhydride derivatives, such as those derived from n-octene and n-decene, were similarly poorly suspended and resulted in unstable dispersions. Without wishing to be bound by theory, the linear conformation of hydrophobic side chains in such polymers is either the binding of hydrophobic surfaces or alternatively the cross-linking between different surfaces. It seems to have made efficiency worse. In either case, aggregation is observed.

  The properties of the copolymers described here are also observed at different dispersant concentrations in WP and WG formulations and show improved storage stability. Also, in many cases, it is possible to reduce the concentration of dispersant below generally accepted levels, and as a result maintain acceptable suspendability and achieve more efficient surface coverage I found out that it was possible. In practical terms, this means that the dispersant is more cost effective for the end user. When comparing the proportion of copolymer used to that of a diisobutylene maleic anhydride sodium salt of similar molecular weight, we generally see that the copolymer of the present invention provides acceptable stability at lower concentrations than the corresponding diisobutylene derivative. I found it. In addition, the formulation generally exhibits improved dispersibility. When compared to sulfonated alkylnaphthalene formaldehyde condensates, the suspendability is significantly improved even at lower concentrations.

  Methods for producing such alternating copolymers will be well known to those skilled in the art of polymer synthesis.

  The dispersant system used in the present invention can be a mixture of alternating copolymers and other dispersants known to those skilled in the art and the like for alkyl-substituted and unsubstituted sulfonated naphthalene formaldehyde condensates. Salts, salts of alkyl-substituted and unsubstituted phenol formaldehyde condensates, lignosulfonated salts, polyacrylate salts, and other previously disclosed α-olefinically unsaturated dicarboxylic acid copolymer derivatives are included.

  In agrochemical applications, a wide variety of insoluble materials, such as active agents, are added to aqueous suspensions. Active active agents such as those used in WP, WG, and SC formulations are generally insoluble at room temperature. Water insoluble materials that are advantageously used in WP, WG, and SC formulations include herbicides, insecticides, fungicides, biocides, snails, algaecides, plant growth regulators, insecticides, rodenticides, Included are nematodes, acaricides, amoebicides, protozoa, crop safners and adjuvants, and the like. Examples of active ingredients usually made as granules or powders for such agriculture are triazine herbicides such as simazine, atrazine, terbutylazine, terbutrin, promethrin, and amethrin, diuron, and fluometron. Urea herbicides, sulfonylurea herbicides such as chlorosulfuron, methylsulfuron methyl, nicosulfuron, and triasulfuron, sulfonanilide herbicides such as flumeturum, organophosphates such as azinephosmethyl, chloropyrifos, sulfrophos and azamethiphos Insecticides, aldicarb, bendiocarb, carbamate insecticides such as carbaryl and BPMC, synthetic pyrethroids such as bifenthrin, as well as dimethomorph, benomyl, carbendazim, mancozeb, hexaconazo Various types of fungicides including triazoles such as Le and diniconazole, include the like acaricides such as propargite. A list of such products can be derived from the Insecticide Dictionary (included in the Agricultural Chemicals Handbook), or the UK Crop Protection Society: Insecticide Manual.

  In addition, chemical fertilizers and also water-soluble active ingredients are used in water-dispersible formulations, added to an inert carrier for operational convenience or to facilitate controlled-release formulations. be able to.

A wide variety of other insoluble materials, including fillers and carriers, are used in agricultural applications such as, but not limited to, natural and synthetic silicates, and silicate minerals, mineral oxides and hydroxides, And there are also natural and synthetically derived organic materials. Such materials are added as porous carriers, as moisture inhibitors, to aid in the binding or agglomeration properties of the formulation, or simply to fill the weight of a convenient formulation. Examples of such fillers include natural silicates such as diatomaceous earth, synthetic precipitated silica, clays such as kaolin, attapulgite and bentonite, zeolites, titanium dioxide, oxidized and iron hydroxide, oxidized and aluminum hydroxide, or Organic materials such as bagasse, charcoal, or synthetic organic polymers. These other insoluble materials can be easily dispersed according to the present invention.
An additional reagent commonly used in combination with the dispersants used in the above formulations is a surfactant as a wetting agent. The role of the wetting agent in the case of SC formulations is to help remove air from the particle surface during production and to facilitate dilution into water. In the case of the WP formulation, the role of the wetting agent promotes the penetration of solids into the water, while in the case of the WG formulation, it promotes the penetration of the granules into the water and promotes the disintegration of the particles to form the primary Return to particle size. In some cases, the dispersant itself can function as a suitable wetting agent, while in other cases, the dispersing agent has an opposite effect to the wetting agent. As a further aspect of the present invention, at least one wet surfactant comprises an alkyl polysaccharide, a di- or monoalkyl sulfosuccinate derivative, a nonionic surfactant loaded on an inert silicate carrier, and a urea interface. Selected from non-ionic surfactants led to the form of activator complexes.

  The process of dispersing the formulation in the aqueous medium is accomplished by any suitable means conventional depending on the nature of the formulation. The dispersion of the formulation in the aqueous solution is preferably done either by hand or with minimal mechanical agitation. Mechanical agitation includes agitation, mixing, blending, and other similar methods.

  Suspensions of insoluble materials in aqueous media are commonly used for the treatment of substrates such as plants or other agricultural substrates. Application of the suspension on the substrate is accomplished by any convenient method, including spraying and the like. Prior to the farmer spraying, the granules are generally dispersed in water. Farmer sprays are done by hand spray on a small back, or by a large boom spray or other convenient method.

  The formulations of the present invention can also be applied directly to the substrate prior to dispersion. Subsequent application of rain or other aqueous media is not particularly problematic for suspension formulations of particulate material.

  The present invention has been described in connection with WP, WG, and SC formulations. In each case, the formulation is provided as a stable aqueous dispersion of finely powdered insoluble hydrophobic particles. The stability properties of the dispersion, and hence the potency of the dispersion, is measured by the method of suspension test described in CIPAC test MT 15.1. In this test, the volume of suspended material and the volume of sediment settled by gravity are compared after 30 minutes. In general, dispersants with a reported percent suspendability of about 80% are considered effective dispersants for WG and WP formulations, while those above 90% are expected for SC formulations . Another measure of dispersion stability is the percentage of particles that remain unagglomerated. This also demonstrates its property of uniformly distributing the dispersant throughout the formulation. The degree of agglomerated particles is often measured by the wet sieve residue test described in CIPAC test MT 59.3. In this test, the dispersed solid is poured into a fine series of sieves and the material retained on the sieve is measured as part of the total amount of dispersed material. Such agglomeration formation is a significant problem observed in WG formulations and to a lesser extent in WP formulations.

  In general, WP formulations are made by grinding the active ingredients alone or in combination with fillers, dispersants and / or wet surfactants to a suitable particle size, generally in the range of 5 to 15 μm. The milled material is then dry blended with a surfactant wetting agent and / or a dispersant or additional dispersant if not present and / or a surfactant wetting agent to form a uniform composition. give. The powder formulation is estimated for its wettability according to the method described in CIPAC MT 53.5.1 and for suspendability according to CIPAC MT 15.1. It is desirable for the formulation to have a wettability of 1 minute or less and a suspendability of 80% or more. Less than 60% is generally considered unacceptable. Market accepted results are measured either by local registered public authorities or by standards set by the formulators themselves.

  In the case of a WG formulation, the active ingredient suitably ground to a particle size of generally 5-15 μm, with or without other fillers, is one or more wet surfactants and one or more dispersants. Mixed. Generally, excess water is added to bind and agglomerate the particles together. Excess water is later reduced to an optimum level by appropriate air drying techniques.

  Agglomerates are generally using one of many techniques well known to those skilled in the art, including bread pulverization, drum pulverization, fluid bed pulverization, spray drying, tableting, or extrusion techniques. Powdered.

  Wetting agents and dispersants are powder blended with the active ingredient, or alternatively as an aqueous solution using a coagulant aid in water. The active ingredient, filler, wetting agent, and dispersant can also be ground together in one operation prior to the addition of water.

  An acceptable WG formulation additionally requires that the granules return to their original dispersed particle size in a short time and are easily dispersed in water. This property is known as dispersibility and, in the description of the present invention, is measured as the time it takes for the granules to disperse in water under standard agitation and return to the original particle size. The dispersion time is preferably 1 minute or less, 20 seconds is excellent, and 2 minutes is inferior. Desirably the granules should also have good suspendability. In general, suspendability is tested using CIPAC MT15.1. 80% or more is a desirable result, and 60% or less is generally not desirable. In many cases when testing particles, so-called maximum surface coverage results are often obtained. This is where the suspension results reach a maximum level from the plateau. The addition of more dispersant is generally not improved as a result. This phenomenon is thought to be due to the particle size distribution of the material. There is usually a given number of particles of such size determined without regard to the type or concentration of dispersant.

  Desirably, the granules should have a low wet sieve retention. Wet sieve retention is generally tested using CIPAC MT59.3. It is desirable that the retained material is 0.1% or less with a 150 μm sieve. More preferably, it is 0.02% or less. Similarly, a value of 0.6% or less is desirable for a 53 μm sieve, and any smaller value is more desirable.

  Further desirable WG formulation properties should be non-dusty and wear resistant. Often this is due to the nature of the pulverization method used and the level of compression obtained here. Often, trade exchanges are observed between the dispersibility characteristics of WG formulations and the level of compression and abrasion resistance. Abrasion resistance is measured by agitating the particles under a set agitation condition and evaluating the level of small particles generated there through various size sieves.

Storage stability was tested by storing at 50 ° C., and tests were conducted at intervals of 1 month or more and at intervals of 3 months to determine what properties were significantly changed.
Preferably, the granules should retain these properties upon storage. Surprisingly, even with extended shelf life, solid formulations such as WP and WG formulations containing dispersants such as those described herein are dispersible and suspended like prior art formulations. There was no influence of deterioration on turbidity.

  We have also found that WP and WG formulations incorporating the dispersants described herein are generally sufficient with less dispersant than currently known WP and WG formulations.

  In the case of WP and WG formulations, as a further aspect of the present invention, the dispersant described herein comprises an alkyl polysaccharide, dialkyl and monoalkyl sulfosuccinate salt, a nonionic surfactant loaded on a porous silicate carrier. And wet surfactants selected from the class consisting of nonionic surfactant urea surfactant complexes. In such formulations, the wetting active can be used in combination at a ratio of 1% w / w or more, and preferably 3% w / w or less. The most preferred wetting agents from the class of alkyl polysaccharides are alkyl polyglucosides, which are derived from the reaction of glucose with a primary hydrocarbon alcohol. More preferred are highly crystalline derivatives such as those obtained from ECOTERIC AS 20 and ECOTERIC AS10 (Orica Australia Pty. Ltd). Most preferred from the monoalkylsulfosuccinate class are the sodium or potassium salts of dicyclohexyl, diisooctyl, and di-n-octylsulfosuccinate. Most preferred in the class of nonionic surfactants loaded on an insoluble, porous silicate carrier is an ethoxylated surfactant loaded on a carrier such as TERIC 157 (Orica Australia Pty Ltd). . The most preferred wetting agent of the urea surfactant complex is a urea adduct of an alcohol ethoxylated surfactant, such as TERWET 7050 (Orica Australia Pty Ltd). The wetting agents described herein have the added advantage of showing good wettability and dispersibility to the formulation and good storage stability in combination with the copolymer dispersants described herein. In contrast, commonly used WG and WP wetting agents such as alkyl naphthalene sulfonate salts and lignosulfonate salts have been found to have poor storage stability.

  In the case of the SC formulations of the present invention, the active ingredient is generally added to the water-containing dispersant, preferably with a surfactant wetting agent along with the usual non-ionic dispersant. Moisturizers are also included in this. The dispersion is formed using high shear mixing. The dispersion is then ground by any one of several wet milling methods and dispersed such that the average particle size of the dispersed solids is 5 μm or less, more typically in the range of 1 to 3 μm. The resulting product is known as millbase and is modified with additives such as antifreezes, thickeners, and anti-settling agents, insecticides, and colorants can also be added. For an acceptable SC formulation, it should not exhibit a high percentage of thickening, settling or agglomeration growth over a period of time. These physical properties are estimated by visual observation.

  SC is generally required to have good viscosity and storage stability. Storage stability is usually estimated as the degree of sedimentation or separation at the top, “claying” that tends to form a precipitate or a sticky layer at the bottom, and “bleeding” that the dispersion tends to separate without the need to exhibit sedimentation. The Redispersibility is also important. These are estimated visually.

  In the case of the dispersants described here, only certain dispersant copolymers are suitable for the SC formulation. When used alone, some dispersant copolymer derivatives give unsuitable viscosities for grinding slurry premixes, so that the dispersants are other fast acting EO / PO block copolymer type dispersants. It is preferable to use in combination with a well-known dispersant such as Without wishing to be bound by theory, it is believed that the dispersant requires time to move to the surface of the dispersed particles. Dispersant copolymers are used in some cases with other known dispersants and work together.

(Best Mode for Carrying Out the Invention)
Although the present invention has been described in relation to agricultural chemical formulations, it is clear that improvements in dispersibility and suspendability are useful in other applications. The invention will be further described in detail with reference to the following non-limiting examples and schemes. All percentages listed herein are weight percentages of the total composition unless otherwise specified.

Example 1
A simazine 900 g / kg WG formulation of the following composition was prepared:
Simazine (Industrial) (98% w / w) 91.8% w / w
MORWET EFW 1.5
(Witco Corp)
Dispersant 6.2
Water 0.5
The dispersant used is a salt of alkyl naphthalene formaldehyde condensate, SCS 2258 (ICI surfactant). The solids were blended with approximately 15% by weight of water to give a plastic premix, which was then extruded using a Fuji-Padal laboratory scale extrusion granulator to prepare granules. The resulting granules were dried using a fluid bed dryer and returned to a moisture content of approximately 0.5% w / w.

  The resulting WG was tested for dispersibility by recording, in seconds, the time required for total disintegration under uniform stirring conditions. Suspension was tested according to CIPAC MT 15.1 and a wet sieve retention test was performed according to CIPAC MT 59.3 using 150 and 53 micron sieves. The results are recorded in Table 1.

Example 2
Simazine 99g / Kg WG was prepared and tested as described in Example 1. The dispersant used here is POLYFON H (Westvaco Corp), a lignosulfonate salt. The results are shown in Table 1.

Example 3
A simazine 900 g / Kg WG formulation with the following composition was prepared:
Simazine (Industrial) (98% w / w) 91.8% w / w
ATPLUS G73050 1.5
(Currently available from Orica Australia Pty LTD under the trademark TERSPERSE 7050)
Dispersant 3.1
Kaolin 3.1
Water 0.5%
The dispersant used was a sodium salt of an alternating copolymer of n-octene and maleic anhydride with a molecular weight of about 20,000 to 30,000. Granules were prepared and tested as described in Example 1. The results are shown in Table 1.

Example 4
Simazine 900 g / Kg WG formulation was prepared and tested according to the method described in Example 3, where the sodium salt of n-decene and maleic anhydride copolymer was used as the dispersant. The results are shown in Table 1.

Example 5
Simazine 900 g / Kg WG formulation was prepared and tested according to the method described in Example 3. Here, as a dispersing agent, diisobutylene having a molecular weight of about 30,000 to 40,000 and a sodium salt of maleic anhydride copolymer were used. The results are shown in Table 1.

Example 6
A WG formulation was prepared and tested as described in Example 3. Here, the sodium salt of SMA 1000 (Atochem Inc.) is used as the dispersant, which is a 1: 1 molar ratio copolymer of styrene and maleic anhydride. The results are shown in Table 1.

Example 7
A WG formulation was prepared and tested as described in Example 3. Here, the sodium salt of SMA 3000 (Atochem Inc.) is used as the dispersant, which is a 3: 1 molar ratio copolymer of styrene and maleic anhydride. The results are shown in Table 1.

Example 8
A WG formulation was prepared and tested as described in Example 3. Here, the sodium salt of GANTREZ AN 119 resin (Rhodia Inc.) is used as a dispersant, which is a copolymer of methyl vinyl ether and maleic anhydride. The results are shown in Table 1.

Example 9
A simazine 900 g / Kg WG formulation of the following composition was prepared:
Simazine (Industrial) (98% w / w) 91.8% w / w
ATPLUS G73050 1.5
(Currently available from Orica Australia Pty LTD under the trademark TERSPERSE 7050)
Dispersant 6.2
Water 0.5%
The dispersant used was a monoammonium salt of an alternating copolymer of diisobutylene and maleic anhydride. Granules were prepared and tested as described in Example 1. The results are shown in Table 1.

Example 10
A simazine 900 g / Kg WG formulation of the following composition was prepared:
Simazine (Industrial) (98% w / w) 91.8% w / w
ATPLUS G73050 1.5
(Currently available from Orica Australia Pty LTD under the trademark TERSPERSE 7050)
Dispersant 3.1
Kaolin 3.1
Water 0.5%
The dispersant used was a sodium salt of an alternating copolymer of undecylenic acid and maleic anhydride. Granules were prepared and tested as described in Example 1. The results are shown in Table 2.

Example 11
Simazine 900 g / Kg WG formulation was prepared and tested according to the method described in Example 10. Here, a sodium salt of an alternating copolymer of vinyl isobutyl ether and maleic anhydride was used as a dispersant. The results are shown in Table 2.

Example 12
Simazine 900 g / Kg WG formulation was prepared and tested according to the method described in Example 10. Here, a sodium salt of an alternating copolymer of alphamethylstyrene and maleic anhydride was used as a dispersant. The results are shown in Table 2.

Example 13
Simazine 900 g / Kg WG formulation was prepared and tested according to the method described in Example 10. Here, a sodium salt of a non-alternating copolymer of alphamethylstyrene: maleic anhydride in a molar ratio of 10: 3 was used as the dispersant. The results are shown in Table 2.

Example 14
Simazine 900 g / Kg WG formulation was prepared and tested according to the method described in Example 10. Here, a sodium salt of a non-alternating copolymer of alphamethylstyrene: maleic anhydride in a molar ratio of 4: 3 was used as a dispersant. The results are shown in Table 2.

Example 15
Simazine 900 g / Kg WG formulation was prepared and tested according to the method described in Example 10. The dispersant used herein was a sodium salt of a non-alternating copolymer of alphamethylstyrene and maleic anhydride made with a 50% molar excess of maleic anhydride. The results are shown in Table 2.

Example 16
Simazine 900 g / Kg WG formulation was prepared and tested according to the method described in Example 10. Here, as a dispersant, benzyltrimethylammonium salt of an alternating copolymer of alphamethylstyrene and maleic anhydride was used. The results are shown in Table 2.

Example 17
Simazine 900 g / Kg WG formulation was prepared and tested according to the method described in Example 10. Here, a sodium salt of an alternating copolymer of d-limonene and maleic anhydride was used as a dispersant. The results are shown in Table 2.

Example 18
Simazine 900 g / Kg WG formulation was prepared and tested according to the method described in Example 10. Here, a sodium salt of an alternating copolymer of β-pinene and maleic anhydride was used as a dispersant. The results are shown in Table 2.

Example 19
Simazine 900 g / Kg WG formulation was prepared and tested according to the method described in Example 10. Here, a sodium salt of an alternating copolymer of dimethyldicyclopentadiene and maleic anhydride was used as a dispersant. The results are shown in Table 2.

Example 20
Simazine 900 g / Kg WG formulation was prepared and tested according to the method described in Example 10. Here, a sodium salt of an alternating copolymer of dicyclopentadiene and maleic anhydride was used as a dispersant. The results are shown in Table 2.

Example 21
A 900 g / kg WG formulation of atrazine having the following composition was prepared.
Atrazine (industrial) (98% w / w) 91.8% w / w
ATPLUS G73050 1.5
(Currently available from Orica Australia Pty Ltd under the trademark TERSPERSE 7050)
Dispersant 3.1
Kaolin 3.1
Water 0.5
The dispersant used here is a sodium salt of an alternating copolymer of dicyclopentadiene and maleic anhydride. Granules were prepared and tested as described in Example 1. The results are shown in Table 2.

Example 22
Atrazine 900 g / kg WG formulation was prepared and tested as described in Example 21. As the dispersant, sodium salt of an alternating copolymer of alphamethylstyrene and maleic anhydride was used. The results are shown in Table 2.

Example 23
A diuron 900 g / kg WG formulation of the following composition was prepared:
Diuron (Industrial) (97% w / w) 92.8% w / w
ATPLUS G73050 1.5
(Currently available from Orica Australia Pty Ltd under the trademark TERSPERSE 3050)
Dispersant 3.1
Kaolin 3.1
Water 0.5
The dispersant used here is a sodium salt of an alternating copolymer of dicyclopentadiene and maleic anhydride. Granules were prepared and tested as described in Example 1. The results are shown in Table 2.

Example 24
A diuron 900 g / kg WG formulation was prepared and tested as described in Example 23. As the dispersant, sodium salt of an alternating copolymer of alphamethylstyrene and maleic anhydride was used. The results are shown in Table 2.

Example 25
A simazine 900 g / kg WG formulation with the following composition was prepared:
Simazine (Industrial) (98% w / w) 91.8% w / w
ATPLUS G73050 1.5
(Currently available from Orica Australia Pty Ltd under the trademark TERSPERSE 7050)
Dispersant 3.1
Kaolin 3.1
Water 0.5
The dispersant used here is a sodium salt of a terpolymer without alternating properties between the first and second comonomers consisting of alphamethylstyrene, styrene, and maleic anhydride. Granules were prepared and tested as described in Example 1. The results are shown in Table 2.

Example 26
Simazine 900 g / kg WG formulation was prepared and tested as described in Example 25. The dispersant used was a sodium salt of a terpolymer that exhibited alternating properties between first and second types of monomers consisting of alphamethylstyrene, dicyclopentadiene, and maleic anhydride. The results are shown in Table 2.

Example 27
Simazine 900 g / kg WG formulation was prepared and tested as described in Example 25. The dispersant used was a sodium salt of a terpolymer exhibiting alternating properties between first and second type monomers consisting of alphamethylstyrene: methacrylic acid: maleic anhydride in a molar ratio of 40:20:40. . The results are shown in Table 2.

Example 28
Simazine 900 g / kg WG formulation was prepared and tested as described in Example 25. The dispersant used was a sodium salt of a terpolymer showing alternating properties between first and second type monomers consisting of alphamethylstyrene: methacrylic acid: maleic anhydride in a molar ratio of 40:10:45. . The results are shown in Table 2.

Example 29
Simazine 900 g / kg WG formulation was prepared and tested as described in Example 25. The dispersant used was a sodium salt of a terpolymer exhibiting alternating properties between first and second type monomers consisting of 48: 2: 48 molar ratio alphamethylstyrene: methacrylic acid: maleic anhydride. . The results are shown in Table 2.

Example 30
Simazine 900 g / kg WG formulation was prepared and tested as described in Example 25. The dispersant is a terpolymer exhibiting alternating properties between first and second type monomers consisting of alphamethylstyrene: 4-vinylpyridine: maleic anhydride in a molar ratio of 37.5: 25: 37.5. The sodium salt of was used. The results are shown in Table 2.

Example 31
Simazine 900 g / kg WG formulation was prepared and tested as described in Example 25. As a dispersant, alternating characteristics between first and second type monomers consisting of alphamethylstyrene: N-vinyl-2-pyrrolidone: maleic anhydride in a 37.5: 25: 37.5 molar ratio. The sodium salt of the indicated terpolymer was used. The results are shown in Table 2.

Example 32
Simazine 900 g / kg WG formulation was prepared and tested as described in Example 25. The dispersant includes a sodium salt of a terpolymer that exhibits alternating properties between first and second types of monomers consisting of 48: 4: 48 molar ratio of alphamethylstyrene: 1-vinylimidazole: maleic anhydride. Using. The results are shown in Table 2.

Example 33
A 900 g / kg WG formulation of atrazine having the following composition was prepared.
Atrazine (industrial) (98% w / w) 91.8% w / w
ATPLUS G73050 1.5
(Currently available from Orica Australia Pty Ltd under the trademark TERSPERSE 3050)
Dispersant 3.1
Kaolin 3.1
Water 0.5
The dispersant used here is a sodium salt of a terpolymer that exhibits alternating properties between first and second types of monomers consisting of alphamethylstyrene, dicyclopentadiene, and maleic anhydride. Granules were prepared and tested as described in Example 1. The results are shown in Table 2.

Example 34
A simazine 900 g / kg WP formulation with the following composition was blended as follows:
Simazine (Industrial) (98% w / w) 91.8% w / w
ATPLUS G73050 1.7
(Currently available from Orica Australia Pty Ltd under the trademark TERSPERSE 3050)
Dispersant 3.1
Kaolin 3.4
The dispersant used is the sodium salt of an alternating copolymer of dicyclopentadiene and maleic anhydride. The results are shown in Table 3. WP wettability was also measured according to CIPAC test MT 53.5.1.

Example 35
A simazine 900 g / kg WP formulation with the following composition was prepared and tested as described in Example 34. The dispersing agent used was 3.1% w / w sodium salt of an alternating copolymer of dicyclopentadiene and maleic anhydride, and the wetting agent was 1.7% w / w sodium salt of dicyclohexylsulfosuccinate. The results are shown in Table 3.

Example 36
Simazine 900 g / kg WP formulation, the wetting agent used was ECOTERIC AS 20 (Orica Australia Pty Ltd), and alkyl polysaccharide was used at 1.7% w / w on active principle (product 50% Prepared and tested as described in Example 34 except for (aqueous solution). The results are shown in Table 3.

Example 37
Simazine 900 g / kg WP formulation, except that the wetting agent used was TERI157 (Orica Australia Pty Ltd) nonionic wetting agent loaded on an insoluble porous carrier used at 1.7% w / w. Prepared and tested as described in Example 34. The results are shown in Table 3.

Example 38
A simazine 900 g / kg WG formulation with the following composition was prepared:
Simazine (Industrial) (98% w / w) 91.8% w / w
Wetting agent 1.5
Dispersant 6.2
Water 0.5%
The dispersant used was a sodium salt of an alternating copolymer of alphamethylstyrene and maleic anhydride, a molecular weight of approximately 20,000-30,000, and the wetting agent used was a MORWET EFW (Witco Corp) sulfonated naphthalene derivative salt. there were. Granules were prepared and tested according to the method described in Example 1. The results are shown in Table 4.

Example 39
Simazine 900 g / kg WG formulation was prepared and tested as described in Example 38. The dispersant used was the sodium salt of an alternating copolymer of alphamethylstyrene and maleic anhydride, and the wetting agent used was the sodium salt of dicyclohexylsulfosuccinate. The results are shown in Table 4.

Example 40
Simazine 900 g / kg WG formulation was prepared and tested as described in Example 38. The dispersant used was the sodium salt of an alternating copolymer of alphamethylstyrene and maleic anhydride, and the wetting agent used was the sodium salt of monocyclohexylsulfosuccinate. The results are shown in Table 4.

Example 41
A 900 g / kg SC formulation of atrazine of the following composition was prepared:
Atrazine (97% w / w for industrial use) 51.5% w / w
Monoethylene glycol 4.0
ATLOX 4896A 3
(Currently available from Orica Australia Pty Ltd under the trademark TERSPERSE 4896)
Dispersant 2
Silicon antifoam 0.2
Rhodopol 23 0.2
(Rhodia Inc)
Proxel GXL 20 0.1
(Zeneca plc)
Water 55.0

  As the dispersant, sodium salt of an alternating copolymer of alphamethylstyrene and maleic anhydride was used. SC dissolves monoethylene glycol, ATLOX 4896A (commercially available under the trademark TERSPERSE 4896, Orica Australia Pty Ltd), and 85% dispersant in water, and atrazine (industrial) and antifoam added with vigorous mixing It is prepared by forming a slurry or mill base. The premix is then kneaded using a laboratory scale bead mill, a Dynomill, so that particles less than 5 microns give a suitable particle size distribution of> 98%. The millbase thus obtained is blended in premix with Proxel GXL 20 (Zeneca plc), and Rodopol 23 (Rhodia Inc) and made up to the desired volume with the remaining water and mixed into a homogeneous mixture. The SC thus obtained is a viscosity that can be used, and with minimal syneresis and thickening, it has been found that it can be stably stored at 2 ° C. to 50 ° C. for up to 1 month storage, and crazing, sedimentation or flocculation Not observed.

Example 42
Attempts were made to make SC formulations according to the formulation and method of Example 41 using 4% w / w sodium salt of alternating copolymer of alpha methyl styrene and maleic anhydride. And only 1% w / w ATLOX 4896A (currently marketed under the trademark TERSPERSE4896, Orica Australia Pty Ltd) was used. The resulting millbase premix had a viscosity that was impossible to knead.

  Those skilled in the art will recognize that the invention described herein is susceptible to variations and modifications other than those explicitly described herein. It should be understood that the invention is subject to all such changes and modifications as fall within the spirit and scope of the invention. The invention also contemplates all of the steps, mechanisms, compositions, and compounds cited or shown herein, individually or collectively, and any and all of any two or more of the steps or mechanisms. Includes combinations.

Claims (21)

A method of dispersing an active water-insoluble pesticide main ingredient in an aqueous solution,
(I) at least one active finely divided solid , water-insoluble pesticide base used in WP, WG or SC formulations and an agriculturally acceptable water-soluble alternating copolymer derivative or agriculturally acceptable Making a formulation comprising at least one dispersant containing possible salts thereof, wherein the alternating copolymer comprises at least one first comonomer residue and at least one second comonomer residue. Wherein the first comonomer is selected from the group consisting of maleic anhydride, or maleic anhydride and methacrylic acid, and the second comonomer is d-limonene, β-pinene, dimethyldicyclopentadiene, dicyclopentadiene or alpha The step comprising methyl styrene, and (ii) the step of dispersing the formulation in an aqueous medium. Including the flop,
Method. 2. The method of claim 1 wherein the alternating copolymer has alternating properties defined as alternating more than 70% consecutive comonomer residue units between the residues of the first comonomer and the second comonomer. The method of claim 1, wherein the alternating copolymer has alternating properties defined as alternating 90% or more consecutive comonomer residue units between the residues of the first comonomer and the second comonomer. The method of claim 1, wherein the alternating copolymer comprises additional comonomer residues that do not substantially alter the alternating properties of the copolymer. The method according to claim 1, wherein the formulation is a WG formulation. Water-insoluble pesticides are herbicides, insecticides, fungicides, biocides, molluscicides, algaides, plant growth regulators, insecticides, rodenticides, nematode control agents, tick control agents, insecticides The method according to any one of claims 1 to 5, which is selected from the group consisting of amoeba, protozoan, fertilizer, crap safener, filler, carrier, and other adjuvants. An agrochemical formulation comprising at least one finely divided solid active water-insoluble agrochemical base and an agriculturally acceptable water-soluble alternating copolymer derivative or an agriculturally acceptable salt thereof At least one dispersant, and the alternating copolymer comprises at least one first comonomer residue and at least one second comonomer residue, wherein the first comonomer is maleic anhydride, or maleic anhydride and A formulation comprising one selected from the group consisting of methacrylic acid, wherein the second comonomer comprises d-limonene, β-pinene, dimethyldicyclopentadiene, dicyclopentadiene or alphamethylstyrene. 8. An agrochemical formulation according to claim 7, wherein the alternating copolymer has alternating properties defined as alternating more than 70% consecutive comonomer residue units between the residues of the first comonomer and the second comonomer. . 8. The agrochemical formulation of claim 7, wherein the alternating copolymer has alternating properties defined as alternating 90% or more consecutive comonomer residue units between the residues of the first comonomer and the second comonomer. . The agrochemical formulation of claim 7, wherein the alternating copolymer comprises additional comonomer residues that do not substantially alter the alternating properties of the copolymer. 8. A pesticide formulation according to claim 7, wherein the dispersant is a derivative of a water-soluble alternating copolymer acceptable for agricultural use, wherein the derivative is selected from the group consisting of polyalkyleneoxy derivatives, polyethylene glycol derivatives, polyamide derivatives and polyvinyl alcohol derivatives. object. The agrochemical formulation according to claim 7, wherein the formulation further comprises a surfactant wetting agent. 13. Agrochemical formulation according to claim 7 or 12, wherein the formulation is a WG formulation. Water-insoluble pesticides are herbicides, insecticides, fungicides, biocides, molluscicides, algaides, plant growth regulators, insecticides, rodenticides, nematode control agents, tick control agents, insecticides 14. The agrochemical formulation according to claim 7 or 13, selected from the group consisting of amoeba, protozoan, fertilizer, crap safener, filler, carrier and other adjuvants. A method for producing a pesticide formulation comprising:
(I) at least one finely divided solid active water-insoluble pesticidal base and at least one derivative of an agriculturally acceptable water-soluble alternating copolymer or an agriculturally acceptable salt thereof Mixing a dispersing agent, wherein the alternating copolymer comprises at least one first comonomer residue and at least one second comonomer residue, wherein the first comonomer is maleic anhydride, or maleic anhydride and A process comprising a methacrylic acid, wherein the second comonomer comprises d-limonene, β-pinene, dimethyldicyclopentadiene, dicyclopentadiene or alphamethylstyrene. 16. A method according to claim 15, wherein the formulation is a WG formulation. Water-insoluble pesticides are herbicides, insecticides, fungicides, biocides, molluscicides, algaides, plant growth regulators, insecticides, rodenticides, nematode control agents, tick control agents, insecticides 16. A method according to claim 15 selected from the group consisting of amoeba, protozoan, fertilizer, crap safener, carrier and other adjuvants. Agricultural preparation produced by the method according to any of claims 15-17. A method of treating a substrate with an active water-insoluble pesticide main ingredient,
(I) a formulation comprising at least one active water-insoluble pesticide base and at least one dispersant containing agriculturally acceptable water-soluble alternating copolymer derivatives or agriculturally acceptable salts thereof. The alternating copolymer comprises at least one first comonomer residue and at least one second comonomer residue, the first comonomer comprising maleic anhydride, or maleic anhydride and methacrylic acid And wherein the second comonomer comprises d-limonene, β-pinene, dimethyldicyclopentadiene, dicyclopentadiene or alphamethylstyrene.
(Ii) dispersing the formulation in an aqueous medium; and (iii) applying the dispersed formulation to a substrate. 20. A method according to claim 19, wherein the formulation is a WG formulation. Water-insoluble pesticides are herbicides, insecticides, fungicides, biocides, molluscicides, algaides, plant growth regulators, insecticides, rodenticides, nematode control agents, tick control agents, insecticides 21. A method according to claim 19 or 20 selected from the group consisting of amoeba, protozoan, fertilizer, crap safener, carrier and other adjuvants.